CN107910515A - A kind of Fe available for negative electrode of lithium ion battery3O4The preparation method of/nitrogen-doped graphene material - Google Patents
A kind of Fe available for negative electrode of lithium ion battery3O4The preparation method of/nitrogen-doped graphene material Download PDFInfo
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- CN107910515A CN107910515A CN201711083222.4A CN201711083222A CN107910515A CN 107910515 A CN107910515 A CN 107910515A CN 201711083222 A CN201711083222 A CN 201711083222A CN 107910515 A CN107910515 A CN 107910515A
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 63
- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 63
- 239000000463 material Substances 0.000 title claims abstract description 32
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 12
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 12
- SZVJSHCCFOBDDC-UHFFFAOYSA-N iron(II,III) oxide Inorganic materials O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 claims abstract description 28
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 28
- 239000008367 deionised water Substances 0.000 claims abstract description 20
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 20
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims abstract description 8
- 239000002994 raw material Substances 0.000 claims abstract description 7
- 150000001875 compounds Chemical class 0.000 claims abstract description 5
- CTENFNNZBMHDDG-UHFFFAOYSA-N Dopamine hydrochloride Chemical compound Cl.NCCC1=CC=C(O)C(O)=C1 CTENFNNZBMHDDG-UHFFFAOYSA-N 0.000 claims abstract description 4
- 229960001149 dopamine hydrochloride Drugs 0.000 claims abstract description 4
- 230000003647 oxidation Effects 0.000 claims abstract description 4
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 4
- 239000002243 precursor Substances 0.000 claims abstract description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 31
- 229920001690 polydopamine Polymers 0.000 claims description 15
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 13
- 239000002131 composite material Substances 0.000 claims description 12
- LENZDBCJOHFCAS-UHFFFAOYSA-N tris Chemical compound OCC(N)(CO)CO LENZDBCJOHFCAS-UHFFFAOYSA-N 0.000 claims description 10
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 8
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 4
- 229910052786 argon Inorganic materials 0.000 claims description 4
- 239000007789 gas Substances 0.000 claims description 4
- FBAFATDZDUQKNH-UHFFFAOYSA-M iron chloride Chemical compound [Cl-].[Fe] FBAFATDZDUQKNH-UHFFFAOYSA-M 0.000 claims description 4
- 235000014413 iron hydroxide Nutrition 0.000 claims description 4
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical group [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 claims description 4
- NCNCGGDMXMBVIA-UHFFFAOYSA-L iron(ii) hydroxide Chemical compound [OH-].[OH-].[Fe+2] NCNCGGDMXMBVIA-UHFFFAOYSA-L 0.000 claims description 4
- 239000001307 helium Substances 0.000 claims description 3
- 229910052734 helium Inorganic materials 0.000 claims description 3
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 claims description 3
- 239000011261 inert gas Substances 0.000 claims description 3
- 238000010438 heat treatment Methods 0.000 claims description 2
- 229910052757 nitrogen Inorganic materials 0.000 claims description 2
- 239000004575 stone Substances 0.000 claims description 2
- 150000001336 alkenes Chemical class 0.000 claims 1
- MVZXTUSAYBWAAM-UHFFFAOYSA-N iron;sulfuric acid Chemical compound [Fe].OS(O)(=O)=O MVZXTUSAYBWAAM-UHFFFAOYSA-N 0.000 claims 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 abstract description 14
- 229910052744 lithium Inorganic materials 0.000 abstract description 14
- 239000002105 nanoparticle Substances 0.000 abstract description 9
- 238000000034 method Methods 0.000 abstract description 7
- 239000000758 substrate Substances 0.000 abstract description 3
- 238000011065 in-situ storage Methods 0.000 abstract 1
- 238000006116 polymerization reaction Methods 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 28
- 238000006243 chemical reaction Methods 0.000 description 16
- 238000003756 stirring Methods 0.000 description 14
- VYFYYTLLBUKUHU-UHFFFAOYSA-N dopamine Chemical compound NCCC1=CC=C(O)C(O)=C1 VYFYYTLLBUKUHU-UHFFFAOYSA-N 0.000 description 9
- -1 oxygen Graphite alkene Chemical class 0.000 description 9
- 239000007983 Tris buffer Substances 0.000 description 8
- 229960003638 dopamine Drugs 0.000 description 8
- 239000006227 byproduct Substances 0.000 description 7
- 238000010792 warming Methods 0.000 description 7
- 150000002823 nitrates Chemical class 0.000 description 4
- 239000002245 particle Substances 0.000 description 4
- 239000003643 water by type Substances 0.000 description 4
- 239000003575 carbonaceous material Substances 0.000 description 3
- 238000000227 grinding Methods 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 239000012300 argon atmosphere Substances 0.000 description 2
- 239000012298 atmosphere Substances 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 229910002804 graphite Inorganic materials 0.000 description 2
- 239000010439 graphite Substances 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- RUTXIHLAWFEWGM-UHFFFAOYSA-H iron(3+) sulfate Chemical compound [Fe+3].[Fe+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O RUTXIHLAWFEWGM-UHFFFAOYSA-H 0.000 description 2
- 229910000360 iron(III) sulfate Inorganic materials 0.000 description 2
- 239000012299 nitrogen atmosphere Substances 0.000 description 2
- WTDRDQBEARUVNC-UHFFFAOYSA-N L-Dopa Natural products OC(=O)C(N)CC1=CC=C(O)C(O)=C1 WTDRDQBEARUVNC-UHFFFAOYSA-N 0.000 description 1
- 239000011149 active material Substances 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000002242 deionisation method Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- MHUWZNTUIIFHAS-CLFAGFIQSA-N dioleoyl phosphatidic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(=O)OCC(COP(O)(O)=O)OC(=O)CCCCCCC\C=C/CCCCCCCC MHUWZNTUIIFHAS-CLFAGFIQSA-N 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 230000003902 lesion Effects 0.000 description 1
- 229960004502 levodopa Drugs 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
Classifications
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/362—Composites
- H01M4/366—Composites as layered products
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
- H01M4/523—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron for non-aqueous cells
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/624—Electric conductive fillers
- H01M4/625—Carbon or graphite
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Composite Materials (AREA)
- Materials Engineering (AREA)
- Nanotechnology (AREA)
- Manufacturing & Machinery (AREA)
- Inorganic Chemistry (AREA)
- Physics & Mathematics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- General Physics & Mathematics (AREA)
- Crystallography & Structural Chemistry (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention belongs to technical field of material, a kind of Fe available for negative electrode of lithium ion battery3O4The preparation method of/nitrogen-doped graphene material.Using two dimensional oxidation graphene as raw material, by Dopamine hydrochloride, in-situ polymerization combined oxidation graphene, acquisition are rich in the graphene complex substrate of electronegativity group in alkaline conditions.Then graphene-based compound is distributed in deionized water, adds molysite precursor, lye is added dropwise and adjusts pH, by controlling the process conditions of lye drop rate and subsequent high temperature processing, realizes Fe3O4Nano particle uniformly loads on nitrogen-doped graphene surface.Raw materials of the present invention enrich, and preparation method controllability is strong.Fe is preferably controlled by the preparation method3O4The growth of nano particle；Obtained Fe3O4Nano particle is dispersed in graphene surface；With prepared Fe3O4/ nitrogen-doped graphene material has more excellent lithium electrical property as lithium cell negative pole material.
Description
Technical field
The invention belongs to technical field of material, is related to a kind of Fe available for negative electrode of lithium ion battery3O4/ N doping
Grapheme material and preparation method thereof.
Background technology
Important component of the negative material as lithium ion battery, directly affects energy density, the circulation longevity of battery
Life and security performance.At present, negative electrode of lithium ion battery is using more mature for carbon-based material, but carbon-based material is because of theoretical capacity
Low, high rate performance difference is difficult to the requirement for meeting high performance lithium ion battery.Therefore the Fe with very high theoretical specific capacity3O4Deng
Inorganic material has obtained the extensive concern of researcher, but Fe3O4Material conductivity is poor, while volume is imitated during discharge and recharge
Substantially it should easily cause coming off for active material, and then lesion electrode.Therefore can be by Fe3O4Material with carbon-based material is compound reaches
Improve the purpose of lithium electrical property.Graphene has superpower electric conductivity and unique texture, can promote quickly to pass applied to lithium battery
Matter, shortens lithium ion diffusion path, can improve the chemical property of lithium ion battery.Shenyang metal institute Li Feng researcher et al.
(Li F, et al., Chemsitry of Materials, 2010,22：5306) stone has been successfully prepared it by carrier of graphene
The black compound Fe of alkene3O4Material, the introducing of graphene have been obviously improved its cycle period and first coulombic efficiency.It is in general, graphene-based
Iron-based oxide composite after hydro-thermal after graphene and the mixing of iron-based presoma and high-temperature process by being made, but this method
Controllability is poor, and the particle stock size homogeneity of formation is poor, and particle and the interaction of graphene carrier be not strong, easily
Come off in charge and discharge process, thus the raising for lithium electrical property is limited.
The content of the invention
The invention reside in provide a kind of Fe available for negative electrode of lithium ion battery3O4The preparation of/nitrogen-doped graphene material
Method, improves the controllability of preparation manipulation so that nano particle is uniformly dispersed in graphene surface, obtains excellent lithium
Electrical property.
The present invention is achieved by the following technical solutions.Using two dimensional oxidation graphene graphene as substrate, in alkaline ring
Under border, by dopamine with forming the graphene complex substrate rich in electronegativity group in its surface aggregate, which is easy to
Combined with the metal ion of positively charged.Then graphene-based compound is distributed in a certain amount of deionized water, is added certain
Molysite precursor is measured, lye, which is added dropwise, with certain speed adjusts pH value of solution, by the rate of addition and high-temperature process that control lye
Process conditions, obtain Fe3O4The dispersed Fe of nano particle3O4/ nitrogen-doped graphene composite material.
Technical scheme：
A kind of Fe available for negative electrode of lithium ion battery3O4The preparation method of/nitrogen-doped graphene material, step are as follows：
(a) 0.5~2mg/mL graphene oxide solutions are configured, add Dopamine hydrochloride, graphene oxide and hydrochloric acid DOPA
The mass ratio of amine is 1:0.5~1:5；The trishydroxymethylaminomethane (Tris) then added adjusts pH value of solution=8.5, room temperature
When lower reaction 12~24 is small, filters, be washed with deionized water into neutrality, dry 12h, obtains poly-dopamine/graphene at 80 DEG C；
(b) poly-dopamine/graphene that step (a) is prepared is raw material, is uniformly dispersed in aqueous, according to oxygen
Graphite alkene and the mass ratio for using molysite precursor are 1:3~1:10 add molysite, by syringe pump with 250~1000 μ
The pH=9 that 1mol/L NaOH solutions adjust whole solution is added dropwise into solution for the speed of L/min, is reacted at room temperature~50 DEG C
12~24h, filters, and neutrality is washed with deionized into, dries 12h at 80 DEG C, obtains iron hydroxide/poly-dopamine/graphene
Composite material；
(c) iron hydroxide/poly-dopamine/graphene composite material that step (b) is prepared is raw material, in indifferent gas
Under body protection, 400~500 DEG C are risen to 1~5 DEG C of heating rate, reacts 1~3h, obtains Fe3O4/ nitrogen-doped graphene material
Material.
The inert gas is nitrogen, argon gas or helium.
The molysite is ferric nitrate, iron chloride or ferric sulfate.
The beneficial effects of the invention are as follows：1) raw materials enrich, and preparation method controllability is strong.The preparation side can be passed through
Method preferably controls Fe3O4The growth of nano particle；2) Fe is obtained3O4Nano particle is dispersed in graphene surface；3) with
Prepared Fe3O4/ nitrogen-doped graphene material has more excellent lithium electrical property as lithium cell negative pole material.
Brief description of the drawings
Fig. 1 is the transmission photo of embodiment 1.
Fig. 2 is the transmission photo of embodiment 3.
Embodiment
Following non-limiting examples can make those of ordinary skill in the art be more fully understood the present invention, but not with
Any mode limits the present invention.
Embodiment 1
Take 50mg graphene oxides to be scattered in the deionized water of 50ml, add 50mg Dopamine hydrochlorides, stir 30min,
Add a certain amount of Tris by solution adjust pH~8.5, then at room temperature reaction 24 it is small when, after reaction, by product spend from
Sub- water is filtered to neutrality, 80 DEG C of dry 12h.Poly-dopamine/graphene complex of acquisition is re-dispersed into 50mL deionizations
In water.Then to 400mg ferric nitrates are added in the solution, after stirring 30min, added using syringe pump with the speed of 250 μ L/min
The NaOH solution for entering 1mol/L adjusts pH~9, reacts 24h under room temperature and neutrality is washed with deionized water into, dried at 80 DEG C
12h。
Tube furnace is put into after the material obtained is ground, is warming up to 500 DEG C in a nitrogen atmosphere with 2 DEG C/min speed,
Then 2h is kept, obtains Fe3O4/ nitrogen-doped graphene composite material.Obtained nano particle is evenly distributed in N doping graphite
Alkene surface, particle diameter are about 10nm or so.As the lithium electrical property measured by lithium cell negative pole material under 100mA/g charge-discharge velocities
Specific capacity is 891.2mAh/g；Its specific discharge capacity under 200mA/g, 500mA/g, 1A/g, 2A/g, 5A/g charge-discharge velocity
Respectively：798.7、720.0、 621.3、511.8、450.7mAh/g.In 2Ag-1Still have after repeating discharge and recharge 200 weeks
The charging and discharging capacity of 492.1mAh/g.
Embodiment 2
Take 100mg graphene oxides to be scattered in the deionized water of 50ml, add 100mg Dopamine hydrochlorides, stirring
30min, adds a certain amount of Tris and solution is adjusted pH~8.5, when then reaction 12 is small at room temperature, after reaction, by product
Filtered with deionized water to neutrality, dry 12h at 80 DEG C.By poly-dopamine/graphene complex be re-dispersed into 50mL go from
In sub- water, then to 1000mg ferric nitrates are added in the solution, after stirring 30min, using syringe pump with the speed of 500 μ L/min
The NaOH solution for adding 1mol/L adjusts pH~9, reacts 12h under the conditions of 50 DEG C, and neutrality is washed with deionized water into, is dried at 80 DEG C
12h。
Tube furnace is put into after the material obtained is ground, is warming up to 500 DEG C under an argon atmosphere with 2 DEG C/min speed,
Then 2h is kept, obtains Fe3O4/ nitrogen-doped graphene composite material.
Embodiment 3
Take 100mg graphene oxides to be scattered in the deionized water of 50ml, add 100mg Dopamine hydrochlorides, stirring
30min, adds a certain amount of Tris and solution is adjusted pH~8.5, when then reaction 24 is small at room temperature, after reaction, by product
Filtered with deionized water to neutrality, dry 12h at 80 DEG C.By poly-dopamine/graphene complex be re-dispersed into 50mL go from
In sub- water, then to 200mg iron chloride is added in the solution, after stirring 30min, using syringe pump with the speed of 1000 μ L/min
The NaOH solution for adding 1mol/L adjusts pH~9, and neutrality is washed with deionized water into reaction 12h under the conditions of 40 DEG C, is dried at 80 DEG C
12h。
Tube furnace will be put into after the material obtained grinding, be warming up to 400 DEG C under argon atmospher with 5 DEG C/min speed, then
1h is kept, obtains Fe3O4/ nitrogen-doped graphene composite material.Obtained nano particle is evenly distributed in nitrogen-doped graphene table
Face, particle diameter are about 20nm or so.As the lithium electrical property measured by lithium cell negative pole material under 100mA/g charge-discharge velocities specific volume
Measure as 580.7mAh/g；Its specific discharge capacity is distinguished under 200mA/g, 500mA/g, 1A/g, 2A/g, 5A/g charge-discharge velocity
For：512.5、414.9、 348.9、281.7、202.5mAh/g.
Embodiment 4
Take 25mg graphene oxides to be scattered in the deionized water of 50ml, add 500mg Dopamine hydrochlorides, stir 30min,
Add a certain amount of Tris by solution adjust pH~8.5, then at room temperature reaction 24 it is small when, after reaction, by product spend from
Sub- water is filtered to neutrality, dry 12h at 80 DEG C.Poly-dopamine/graphene complex is re-dispersed into 50mL deionized waters.
Then to 75mg iron chloride is added in the solution, after stirring 30min, added using syringe pump with the speed of 1000 μ L/min
The NaOH solution of 1mol/L adjusts pH~9, reacts 24h at room temperature and neutrality is washed with deionized water into, 12h is dried at 80 DEG C.
Tube furnace will be put into after the material obtained grinding, be warming up to 400 DEG C under argon gas atmosphere with 1 DEG C/min speed, so
After keep 1h, obtain Fe3O4/ nitrogen-doped graphene composite material.
Embodiment 5
Take 50mg graphene oxides to be scattered in the deionized water of 50ml, add 100mg Dopamine hydrochlorides, stir 30min,
Add a certain amount of Tris by solution adjust pH~8.5, then at room temperature reaction 12 it is small when, after reaction, by product spend from
Sub- water is filtered to neutrality, dry 12h at 80 DEG C.Poly-dopamine/graphene complex is re-dispersed into 50mL deionized waters.
Then to 500mg ferric sulfate is added in the solution, after stirring 30min, added using syringe pump with the speed of 500 μ L/min
The NaOH solution of 1mol/L adjusts pH~9, reacts 24h at room temperature and neutrality is washed with deionized water into, 12h is dried at 80 DEG C.
Tube furnace is put into after the material obtained is ground, 400 DEG C are warming up to 2 DEG C/min speed under helium atmosphere,
Then 3h is kept, obtains Fe3O4/ nitrogen-doped graphene composite material.
Embodiment 6
Take 50mg graphene oxides to be scattered in the deionized water of 50ml, add 50mg Dopamine hydrochlorides, stir 30min,
Add a certain amount of Tris by solution adjust pH~8.5, then at room temperature reaction 24 it is small when, after reaction, by product spend from
Sub- water is filtered to neutrality, dry 12h at 80 DEG C.Poly-dopamine/graphene complex is re-dispersed into 50mL deionized waters.
Then to 150mg ferric nitrates are added in the solution, after stirring 30min, added using syringe pump with the speed of 250 μ L/min
The NaOH solution of 1mol/L adjusts pH~9, reacts 24h at room temperature and neutrality is washed with deionized water into, 12h is dried at 80 DEG C.
Tube furnace is put into after the material obtained is ground, is warming up to 500 DEG C under an argon atmosphere with 3 DEG C/min speed,
Then 2h is kept, obtains Fe3O4/ nitrogen-doped graphene composite material.
Embodiment 7
Take 50mg graphene oxides to be scattered in the deionized water of 50ml, add 150mg Dopamine hydrochlorides, stir 30min,
Add a certain amount of Tris by solution adjust pH~8.5, then at room temperature reaction 24 it is small when, after reaction, by product spend from
Sub- water is filtered to neutrality, dry 12h at 80 DEG C.Poly-dopamine/graphene complex is re-dispersed into 50mL deionized waters.
Then to 300mg ferric nitrates are added in the solution, after stirring 30min, added using syringe pump with the speed of 500 μ L/min
The NaOH solution of 1mol/L adjusts pH~9, reacts 24h at room temperature and neutrality is washed with deionized water into, 12h is dried at 80 DEG C.
Tube furnace will be put into after the material obtained grinding, be warming up to 500 DEG C under nitrogen atmosphere with 2 DEG C/min speed, so
After keep 2h, obtain Fe3O4/ nitrogen-doped graphene composite material.Exist as the lithium electrical property measured by lithium cell negative pole material
Specific capacity is 795.8mAh/g under 100mA/g charge-discharge velocities；In 200 mA/g, 500mA/g, 1A/g, 2A/g, 5A/g discharge and recharges
Its specific discharge capacity is respectively under speed：650.2、 578.5、490.9、422.3、345.4mAh/g.
Claims (3)
- A kind of 1. Fe available for negative electrode of lithium ion battery3O4The preparation method of/nitrogen-doped graphene material, it is characterised in that step It is rapid as follows：(a) configuration 0.5~2mg/mL graphene oxide solutions, addition Dopamine hydrochloride, graphene oxide and Dopamine hydrochloride Mass ratio is 1:0.5~1:5；The trishydroxymethylaminomethane then added adjusts pH value of solution=8.5, reacts 12~24 at room temperature Hour, filter, neutrality is washed with deionized water into, dries 12h at 80 DEG C, obtains poly-dopamine/graphene；(b) poly-dopamine/graphene that step (a) is prepared is raw material, is uniformly dispersed in aqueous, according to oxidation stone Black alkene and the mass ratio for using molysite precursor are 1:3~1:10 add molysite, by syringe pump with 250~1000 μ L/min Speed the pH=9 that 1mol/L NaOH solutions adjust whole solution is added dropwise into solution, react 12 at room temperature~50 DEG C~ 24h, filters, and neutrality is washed with deionized into, dries 12h at 80 DEG C, it is compound to obtain iron hydroxide/poly-dopamine/graphene Material；(c) iron hydroxide/poly-dopamine/graphene composite material that step (b) is prepared is raw material, is protected in inert gas Under shield, 400~500 DEG C are risen to 1~5 DEG C of heating rate, reacts 1~3h, obtains Fe3O4/ nitrogen-doped graphene material.
- 2. preparation method according to claim 1, it is characterised in that the inert gas is nitrogen, argon gas or helium.
- 3. preparation method according to claim 1 or 2, it is characterised in that the molysite is ferric nitrate, iron chloride or sulfuric acid Iron.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201711083222.4A CN107910515B (en) | 2017-11-07 | 2017-11-07 | Fe capable of being used for lithium ion battery cathode3O4Preparation method of/nitrogen-doped graphene material |
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| CN109728290A (en) * | 2019-01-25 | 2019-05-07 | 安徽益佳通电池有限公司 | A kind of preparation method and applications of transition metal oxide/graphitized intermediate-phase carbosphere composite material |
| CN109741964A (en) * | 2019-02-18 | 2019-05-10 | 南阳理工学院 | Iron oxide-poly-dopamine-graphene composite material, preparation method and application |
| CN111252753A (en) * | 2018-11-30 | 2020-06-09 | 中国科学院大连化学物理研究所 | Three-dimensional ordered porous nitrogen-doped graphene and preparation method and application thereof |
| CN111403701A (en) * | 2020-03-09 | 2020-07-10 | 南京邮电大学 | Preparation method of iron-based compound composite nitrogen-doped graphene sodium-ion negative electrode battery material |
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| CN113362985A (en) * | 2021-06-30 | 2021-09-07 | 深圳市正蓝实业有限公司 | Nano rare earth thick film electronic paste and preparation method thereof |
| CN113479871A (en) * | 2021-07-30 | 2021-10-08 | 绍兴文理学院 | Preparation method of in-situ self-growth-based ultra-small metal oxide nanoparticle modified graphene |
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| CN112768678B (en) * | 2019-11-05 | 2024-09-17 | 贝特瑞新材料集团股份有限公司 | Negative electrode material, preparation method thereof and lithium ion battery |
| CN111403701B (en) * | 2020-03-09 | 2022-07-26 | 南京邮电大学 | Preparation method of iron-based compound composite nitrogen-doped graphene sodium ion negative electrode battery material |
| CN111403701A (en) * | 2020-03-09 | 2020-07-10 | 南京邮电大学 | Preparation method of iron-based compound composite nitrogen-doped graphene sodium-ion negative electrode battery material |
| CN111863462A (en) * | 2020-07-10 | 2020-10-30 | 大连理工大学 | Ferroferric oxide/nitrogen-doped hollow carbon sphere composite material for supercapacitor and preparation method thereof |
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| CN113479871B (en) * | 2021-07-30 | 2023-03-28 | 绍兴文理学院 | Preparation method of in-situ self-growth-based ultra-small metal oxide nanoparticle modified graphene |
| CN114068896A (en) * | 2021-11-01 | 2022-02-18 | 广东佳纳能源科技有限公司 | Composite material and preparation method thereof |
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